Composition of matter and method of making same



Patented Mar. 27, 1945 "UNITED STATE s PATENT OFFICE coMPosiTioNoF MATTER AND METHOD OF MAKING SAME Melvin De Groote, University City, and Bernhard Keiser, Webster-Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, DeL, a corporation of Delaware No Drawing.

Original application June 23, 1943,

' Serial No. 492,184. Divided and this application April 7,1944, Serial No. 530,046

9 Claims) (01. 260-402) material or composition of matter, that is par-' ticularly'adapted for use'as a demulsifier in the resolution of crude oil emulsions.

Another object of our invention is to provide a novel method for producing'said new matev,

rial or composition of matter.

Briefly described, our new chemical product consists of the sulfonic acid or sulfonic acid salts or esters of an arylalkanol r aryloxyalkanol, in which there is at least one nuclearly-linked fatty acid radical derived from an unsaturated fatty acid having at least 11 and not over 22 carbon atoms.

Considered in a broad generic sense, the type of aryl sulfonic acid just described may be referred to as a Twitchell agent, or sulfo-fatty aromatic acid, or sometimes as a sulfo-aromatic fatty acid. Prior reference to the ester form concerns the carboxyl radical and not the sulfonic acid radical, as is apparent in light of subsequent description. One of the common procedures em,- ployed to manufacture sulfoaromatic fatty acids, is to employ a method in which the selected aromatic material and the selected unsaturated fatty acid, such as oleic acid, are subjected to a sulfonation-condensation reaction. Such reaction involves a simultaneous introduction of the fatty acid radical into the aromatic nucleus, along with the simultaneous introduction of one or more sulfonic acid radicals. Thus, it is our preferred pro... cedure to manufacture the herein contemplated compounds in'the manner thus indicated.

ample, ethylene oxide, propylene oxide, butylene oxide, glycide, or the equivalent.

Although a monocyclic aryl reactant or alcohol may be employed, such as phenylethanol or phenoxyethanol, it is our preference to employ reactants in which there is present a polycyclic aryl nucleus, rather than a monocyclic aryl nucleus. Such hydroxylated aryl compound, that is, either the phenol or the aromatic alcohol, or perhaps, more correctly, the aryl alkanol a1- cohol, was treated with three to ten moles of a More specifically, the procedure employed is glycide alcohol, ethylene oxide, 'proplene oxide,'.

butene-2 oxide, butene-l oxide, isobutylene oxide, butadiene oxide, butadiene dioxide, chloroprene oxide, isoprene oxide, decene oxide, styrene oxide, cyclohexylene oxide, cyclopentene oxide, etc.

Our preference isto use an alkylene oxide having' not more than four carbon atoms, as, for ex-' suitable oxyalkylating agent, and particularly, one having not'over four carbon atoms, for instance, ethylene oxide, propylene oxide, butylene oxide, or glycid. It is our preference to use an amountof ethylene oxide so that the compound,

in absence of a sulfonic acid radical, and in absence of a neutralized carboxyl radical, would not be water-soluble. In other words, we particularly contemplate the type of compound in which the sulfonic acid radical alone, or in combination with theneutralized carboxyl radical, contributes, a significant part of the hydrophile property of the finished compound. The simplest manufacturing procedure involves the selection of a suitable aryl material, such as orthophenylphenol, paraphenylphenol, p-tert-amylphenoxy ethanol, di-tert amylphenoxy ethanol, beta (ptert butylphenoxy) ethanol, l-tert butyl-zphenylphenol beta-phenoxy ethanol, phenyl ethanol, naphthyl ethanol, phenyl propanol, benzyl alcohol, phenylphenol, phenylclohexanol, as a first step. Such aromatic reactant, that is,

the aryl alkanol, or the aryl oxylkanol, is treated with approximately 3 to 11 moles of an alkylene Such procedure is Well known. The aryl polyglycol so obtained is subjected to a sulfonationcondensation reaction of the kind previously described, in which an unsaturated fatty acid is present as a reactant and oleum or the equivalent is used as the sulfonating and condensin agent. The following examples will serve to illustrate such procedure.

ARYL PoLYcLYcoL Example 1 Hydroxy di-phenyl is reacted in the customary manner with 3' to 10 moles of ethylene oxide, so as to produce the aryl polyglycol.

ARYL POLYGLYCOL Example 2 One mole of benzyl alcohol is reacted with ethylene oxide in the same manner as in the preceding example.

ARYL POLYGLYCOL Example 3 One pound mole of *naphthyl ethanol is reacted with ethylene oxide in the manner indicated in the preceding Example 1.

.ARYL POLYGLYCOL Example 4 One pound mole of betanap'hthol 'is' reacted with ethylene oxide in the manner described in Example 1, preceding.

ARYL POLYGLYCOL Example '5 One pound mole of 4-tert-butyl-2-pheny1phe- 1101 is treated with ethylene oxide in thesame manner as described in Example 1 preceding.

Asxi. Popxcnxcor.

Example 6 The same procedure .islfol-lowed .as.in Examples scribed sulfoaromatic fatty acids arehigher unsaturated fatty acidspas exemplified by oleic .acid. These unsaturatedfatty acids vary .in'the number ,of carbon atoms. present,,fr.om .11 to .22. .For instance, unsaturated acids havinglll carbon atoms may be obtained by pyrolysis of caster-oil or .ricinoleic acid.. Similar acids .having asmany as '20 to 22 carbon acids, are ,.obtainable from jojoba bean oil, or from othernaturally-occurring Waxes. Better known examples are oleic acid, erucic acid, and the like. Someof the fatty acids may contain more than one ethylene-linkage, as, for example, linoleic acid, or linOlenic acid. Furthermore, one mayemploy "a naturallyoccurring mixture of fatty acids, rather than a single. specific acid. .Our preference is to employ the mono-ethylenic acids.

SULFOAROMATIO COMPOUND Example .1

One pound mole of phenOlphenol-is treated with ethylene oxide, as in preceding-aryl polyglycol, Example 1, and the oxyalkylated derivative .is mixed with onepound mole of oleic acid -hydrogen-hydrogen sulfate, prepared by reactthat both the sulfonation reaction and the condensation reaction are complete. A reaction temperature as high as 75 'C. "can be employed, if need be. The sulfonated mass :is then-diluted with water until it ,showsa tendencysto separate readily. It is then permitted to remain in a quiescent state, until such separation is com plete. drawn. The acidic mass is neutralized with a suitable base so as to convert the sulfonic acid radical into the salt form. The carboxylic hydrogen atom is permitted to remain unneutralized. Generally speaking, this means neutralization to the methyl orangeend point. Any suitable base may be employed. Such basic materials include "caustic soda, caustic potash, ammonium hydrate, triethanolamine, oxyethylated triethanolamine, derived by treating triethanolamine with ethylene oxide and oxyethylated tris- (hydroxymethyl) aminomethane, derived by treatment of tris(hydroxymethyl) aminomethane with ethylene oxide. These bases enhance Water .solubility.

SULFOAROMATIC COMPOUND Example 2 One pound mole of 4-tert butyl-2-phenylphenol is substituted for one pound mole of hydroxy phenylphenol in Example 1, preceding.

bled, .due to the presence of the two reactive hydroxylradicals.

SUtFO'ARoi/mrrc COMPOUND Example '5 z The same procedure is followed as in Examples 1 to 4, preceding, except that un'decylenicacid is substituted for oleic acid in the preceding Examples 1 to 4, inclusive.

'SULFOAROMATIC COMPOUND I Example 6 I I I The same ,procedureis employed as in Examples '1, to 4, preceding, except that euricic acid is substituted for oleic acid.-

SULFOAROMATI COMPOUND Example 7 The same procedure is followed as in Examples 1 to 4, preceding, except that the mixed .fatty acids derived from sunfiowerseed Oil or teaseed oil is used instead o'foleic acid.

SULFOAROMATIC COMPOUND Example 8 The same procedure is followed as in Examples 1 to 'l,- preceding, except that the acidic mass is employed as such, or after neutralization-wither base which tends to reduce water solubility, and in fact, may result in a compound which is either oil-soluble, or almost water-"insoluble, or completely water-insoluble, or may show extreme insolubility in either water or 011. Among the suitable-bases for such purposes are: Pyridine, cyclohexylamine, dicyclohexylamine, benzylamine, dibenzylamine, amylamine, diamylamine, triamy'lamine, octadecylamine, and particularly high The lower layer of dilute acid is withmolal amines, which, in theform of the acetate,

show surface activity. j

SULFOAROMATIC COMPOUND Example 9 show surface-activity in aqueous solution. Generally speaking, such quaternary compoundsare more apt to be available in the form of salts, for instance, a chloride or bromide, rather than in the form of the free base.v In the light of this fact, salts of the kind herein 'contemplatedJ. e., sulfonates, are best obtained metathetioally. The two conventional procedures forsuch metathetical reactions involve preparing the sodium, potassium, the ammonium salt of the sulfonic acids previously described, and then reacting an alcoholic solution of such salts with an alcohol solution of the quaternary chloride or bromide. Another procedure involves the principle that the combination of a surface-active anion and surface-active cation is apt to produce a salt which i is insoluble in water, in the absence'of an excess of either reactant. Thus, an aqueous solution of the sodium, potassium, or ammonium salt of the kind described .inv the. preceding examples may be reacted. in dilute solution, for instance, with a 5% soution of cetyl pyridinium bromide, or any one of a number of other surface-active quaternary halides, as, for example, those described in our co-pending application Serial No. 463,439, filed October 26, 1942. I

Incidentally, in the various examples, the car,- boxyl radical may be converted into the salt form by neutralization with any of the indicated bases. Previous reference has been made to the fact that the carboxyl radical may be converted from the free acid form into salt or anester. When resultantis concerned. At this point this acidic mass, priorto dilution, is mixed with a low molal alcohol, such as ethyl alcohol, propyl alcohol,

converted into an ester, the carbon radical which replaces the ionizable hydrogen atom may be derived from an aliphatic alcohol, an alicyclic alcohol, such as methyl alcohol, ethyl alcohol,

propyl alcohol, butyl alcohol, amyl alcohol, octyl alcohol, decyl alcohol, oreven a high molal alcohol, such as hexadecyl alcohol, octadecyl alcohol, etc, or any isomer thereof, and permit esterificav tion to take place by reaction with the carboxyl radical. The sulfuric acid or oleum used as a sulfonation-condensationv agent, also acts as an esterifying agent to permit the indicated reaction. It is probable that the reaction is also accelerated by the presence of a large amount of sulfonic acid. Other alcohols, such as alicyclic alcohols, aralkyl alcohols, including benzyl alcohol, ethylbenzyl alcohol, cyclohexyl alcohol, ethylcyclohexyl alcohol. etc.,.may be used for such esterification reaction.

SULFOAROMATIC COMPOUND Example 10 The same procedure is followed as in the preceding examples, insofar as the production of the acidic mass, containing the sulfoaromatic butyl alcohol, or the like, in such amounts that there is present at least two moles ofthe selected alcohol for each carboxylradical. The acidic mass is stirred until uniform, and then sulfuric acid, 96% strength, is added in amounts equivalent to 3 moles of sulfuric acid for each mole of alcohol added. The alcohols added are anhydrous, or preferably, substantially anhydrous. The acidic mass so obtained is permitted to stand ,forapproximately 3 to 1.0 days at approximately 20-.-35 C,,until the esteriflcation reaction is sub- I .s'tantially complete, as indicated by substantial disappearance of free 'carboxyl radicals. The acidic mass is then separated in the conventional manner previously described, and the sulfonic acid radical and any residual carboxyl radical present are neutralized byv means of any one of the bases previousy indicated, which may be of ,the type that enhance ,water solubilityf'lhe excess of low molal alcohol present is permitted to remain or be removed by distillation. v r

I It is to be noted that in the polycyclic aryl compounds described, that one may employ either the condensed polycyclic type or the isolated type.

We do, not, however, contemplate the type of compound obtained from a reactant in which the aryl nuclei are separated by a non-aryl carbon atom; as, for'example, in diphenylol dime thyl methane. In light of what has been said, numerous other means or procedures may be'employed for manufacturing the compounds herein contemplated. For instance, one can obtain hyinvolve the sulfonic acid radical so that the sulfonic acid isconverted into a glycol or polygly- 'col ester having a residual hydroxyl radical.

Reference is made to the following patents which are concerned with the production of sulfoaromatic fatty acids or compounds which can be readily converted into the same by sulfonation: U. S. Patents Nos. 1,642,595, dated Sept. 13, 1927;

1,779,345 dated Oct. 21, .1930; and 2,302,070 dated Nov. 17,1942; British Patents Nos. 286,796 dated Mar. is, 1928; and 454,183 dated Sept. 25, 1936;

German Patents Nos. 492,508 dated Feb. 6, 1930;

538,762 datedNov. 5, 1931; 589,508 dated Nov. 23,

1933; 663,983 dated July 28, 1938; and 678,134 dated July 8, 1939.

Summarizing what has been said, the type of aryl polyglycol sulfonic acid contemplated herein may be exemplified by the following formula:

[ Hilts 114000.11:

in which R1 is an aryl radical, Ra-RzCOO-is number varying from 3 to 10- and m represents the numeral zero, one .or two, with the proviso that there must be at least one occurrence of a polyglycol radical containing at least} oxygen whether the nuclear hydrogen atom attaches itself to radical R2 and the aryl radical to R3, or in versely, the hydrogen atom to R3 and the aryl radical to R2. One form is simply the metamer of the other form. Any isomeric or metameric form is equally satisfactory. It is understood that the formulas in the hereto appended claims include all isomeric, and particularly, all metameric.forms. An ordinary oleic acid ethylene linkage appears at the 9-10 carbon atom position. With other unsaturated acids the position might vary. The formula brings out clearly thefact that the fatty acid radical is nuclearly linked. so as to present a branch chain arrangement.

, Chemical products or compounds of the kind above described, are adapted to be used as de- ,mulsifiers in the resolution of petroleum emulsions of the water-in-oil type they are adapted to be used in the removal of a residual mud sheath which remains after drilling a well by the rotary method; they may be used as a break inducer in doctor treatment of the kind intended to sweeten gasoline; certain of said productsare of value as surface tension depressants in the acidification of calcareous oil-bearing strata by means of a strong mineral acid, such as hydrochloric acid; and some of said products are capable of use as wetting agents in the flooding of exhausted oil-bearing strata, and for various other uses where wetting agentsof the conventional type are employed. As to some of such uses which are well known. see .The expanding application of wetting agents,

Chemical Industries, volume 48, page 324 (1941) 1 Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

A new chemical product, comprising an aryl polyglycol sulfonate of the formula:

in which R1 is an aryl radical,

- "2. A new chemical product, comprising an aryl polyglycol sulfonate of the formula:

SOalVI 3.1a I: -R1[0'(o,.'Hz,.0),..H]m'

R40 0 C R2 lcnHanowflnzflomnla in which R1 is a polycyclic aryl radical,

is the fatty acid residue of the unsaturated higher fatty acid, R3=R2COOH, and R4 is a member of the class consisting of aliphatic hydrocarbon radicals and cations including hydrogen; M is a cation including hydrogen; 1:. is a'small whole number greater than one and not in excess of ten; m is a small whole number varying from 3 to 11, and 172' represents the numeral zero, one or two, with the proviso that there must be at least one occurrence of a polyglycol radical containing at least 4 oxygen atoms, including the hydroxyl oxygen atom.

'13. A new chemical product, comprising an aryl polyglycol 'sulf'onate of the formula:

in which R1 is a polycyclic aryl radical in which the nuclei are isolated,

liar-12000 is the fatty acid residue of the unsaturated higher fatty acid, R3:R2COOH, and R4 is a member of the class consisting of aliphatic hydrocarbon radicals and cations including hydrogen; M is a cation including hydrogen; n is a small whole number greater than one and not in excess of ten; m is a small whole number varying from 3 to 1l, and m represents the numeral zero, one or two, with the proviso that there must be at least one occurrence of a polyglycol radical containing at least 4 oxygen atoms, including the hydroxyl oxygen atom.

4. Anew chemical product, comprising an aryl polyglycol sulfonate of the formula:

in which'Rl is a polycyclic aryl radical in which the nuclei are isolated,

is the fatty acid residue of the unsaturated 18 carbon atom fatty acid, R3=R2COOH, and R4 is a member of the class consisting of aliphatic hydrocarbon radicals and cations including hydrogen; M is a cation including hydrogen; n is a small whole number greater than one and not in excess of ten; m is a small whole number varying from 3 to 11, m represents the numeral zero, one or two, with the proviso that there must be at least one occurrence of a polyglycol radical containing at least 4 oxygen atoms, including the hydroxyl oxygen atom.

5. A new chemical. product, comprising an aryl polyglycol sulfonate of the formula:

in which R1 is a polycyclic aryl radical in which the nuclei are isolated,

l 'ti-1 hCOO is the fatty acid residue of the unsaturated 18 carbon atom fatty acid, R3=R2COOH, and R4 is a member of the class consisting of aliphatic hydrocarbon radicals and cations including hydrogen; M is a cation including hydrogen; m

is a small whole number varying from 3 to 11,

and m represents the numeral zero, one or two, with the proviso that there must be at least one occurrence of a polyglycol radical containing at least 4 oxygen atoms includingthe hydroxyl oxyen atom.

6. A new chemical product, comprising an aryl polyglycol sulfonate of the formula:

SOiM I: H.Ra

R4OOG.R2

[O(C:H40) H1 in which R1 is a polycyclic aryl radical in which thenuclei are isolated,

is the fatty acid residue of the unsaturated 18 carbon atom fatty acid, R3=R2COOH, and R4 is a member of the class consisting of aliphatic hydrocarbon radicals and cations including hydrogen; M is a cation including hydrogen; and m is asmall whole number varying from 3 to 5.

7. A new chemical product, comprising an aryl polyglycol sulfonate of the formula:

in which R1 is a polycyclic aryl radical in which the nuclei are isolated,

is the fatty acid residue of the unsaturated 18 carbon atom fatty acid, R3=R2COOH, and R4 is a member of the class consisting of aliphatic hydrocarbon radicals and cations including hydrogen; M is a cation including hydrogen; and m is a small whole number varying from 6 to 8.

8. A new chemical product, comprising an aryl polyglycol sulfonate of the formula:

in which R1 is a polycyclic aryl radical in which the nuclei are isolated,

is the fatty acid residue of the unsaturated 18 carbon atom fatty acid, R3=R2COOH, and R4 is a member of the class consisting of aliphatic hydrocarbon radicals and cations including hydrogen; M is a cation including hydrogen; and m is a. small whole number varying from 9 to 11.

9. In a method of manufacturing aryl polyglycol sulfonates, as described in claim 1, the steps of (a) subjecting a member of the class consisting of arylalkanols and aryloxyalkanols to oxyalkylation (b) subjecting said oxyalkylated derivatives to a condensation sulfonation reaction in the presence'of an unsaturated higher fatty acid by reaction with and in presence of an excess of sulfuric acid, (0) admixing the acid reaction mass with suflicient water so as to cause an incipient tendency to separate, and (d) permitting said water diluted acidic mass to stand in a quiescent state until separation is complete with subsequent withdrawal of dilute acid.

MELVIN DE 'GROOTE. BERNHARD KEISER. 

